In Situ Formation of Li 2 SiO 3 -Li-NaCl Interface on Si and Its Effect on Hydrogen Evolution.

Silicon has emerged as a competitive candidate for hydrolytic hydrogen production due to its high theoretical hydrogen yield, low cost, and on-demand availability. However, the hydrolysis reaction is extremely restrained by passivated SiO 2 , including the original one on the Si surface and the generated one during hydrolysis, and almost no hydrogen is produced in pure water. Herein, the original SiO 2 surface has been effectively removed by milling micro-Si mixed with a small amount of Li metal and NaCl. An artificial soluble interface on Si has been established containing Li 2 SiO 3 , Li, and NaCl. Once micro-Si is placed into water, fresh Si surface can be exposed and a weak LiOH solution can be generated due to the fast dissolution of the interface layer, resulting in the rapid liberation of hydrogen gas. Accordingly, the modified micro-Si displays a significantly enhanced hydrogen production in pure water at 30 °C (1213 mL g -1 H 2 within 3.0 h), which is 2.0 and 4.7 times higher than that observed for ball-milled Si and raw Si in 0.06 M LiOH solution, respectively. In addition, it also exhibited an outstanding operation compatibility for practical uses. This work has proposed a green, effective, and scalable strategy to promote hydrogen production from the hydrolysis of Si-based systems.